SummaryThe emergence of life is one of the most fascinating and yet largely unsolved questions in the natural sciences, and thus a significant challenge for scientists from many disciplines. There is growing evidence that ribonucleic acid (RNA) polymers, which are capable of genetic information storage and self-catalysis, were involved in the early forms of life. But despite recent progress, RNA synthesis without biological machineries is very challenging. The current project aims at understanding how to synthesize RNA in abiotic conditions. I will solve problems associated with three critical aspects of RNA formation that I will rationalize at a molecular level: (i) accumulation of precursors, (ii) formation of a chemical bond between RNA monomers, and (iii) tolerance for alternative backbone sugars or linkages. Because I will study problems ranging from the formation of chemical bonds up to the stability of large biopolymers, I propose an original computational multi-scale approach combining techniques that range from quantum calculations to large-scale all-atom simulations, employed together with efficient enhanced-sampling algorithms, forcefield improvement, cutting-edge analysis methods and model development.
My objectives are the following:
1 • To explain why the poorly-understood thermally-driven process of thermophoresis can contribute to the accumulation of dilute precursors.
2 • To understand why linking RNA monomers with phosphoester bonds is so difficult, to understand the molecular mechanism of possible catalysts and to suggest key improvements.
3 • To rationalize the molecular basis for RNA tolerance for alternative backbone sugars or linkages that have probably been incorporated in abiotic conditions.
This unique in-silico laboratory setup should significantly impact our comprehension of life’s origin by overcoming major obstacles to RNA abiotic formation, and in addition will reveal significant orthogonal outcomes for (bio)technological applications.

The emergence of life is one of the most fascinating and yet largely unsolved questions in the natural sciences, and thus a significant challenge for scientists from many disciplines. There is growing evidence that ribonucleic acid (RNA) polymers, which are capable of genetic information storage and self-catalysis, were involved in the early forms of life. But despite recent progress, RNA synthesis without biological machineries is very challenging. The current project aims at understanding how to synthesize RNA in abiotic conditions. I will solve problems associated with three critical aspects of RNA formation that I will rationalize at a molecular level: (i) accumulation of precursors, (ii) formation of a chemical bond between RNA monomers, and (iii) tolerance for alternative backbone sugars or linkages. Because I will study problems ranging from the formation of chemical bonds up to the stability of large biopolymers, I propose an original computational multi-scale approach combining techniques that range from quantum calculations to large-scale all-atom simulations, employed together with efficient enhanced-sampling algorithms, forcefield improvement, cutting-edge analysis methods and model development.
My objectives are the following:
1 • To explain why the poorly-understood thermally-driven process of thermophoresis can contribute to the accumulation of dilute precursors.
2 • To understand why linking RNA monomers with phosphoester bonds is so difficult, to understand the molecular mechanism of possible catalysts and to suggest key improvements.
3 • To rationalize the molecular basis for RNA tolerance for alternative backbone sugars or linkages that have probably been incorporated in abiotic conditions.
This unique in-silico laboratory setup should significantly impact our comprehension of life’s origin by overcoming major obstacles to RNA abiotic formation, and in addition will reveal significant orthogonal outcomes for (bio)technological applications.

Max ERC Funding

1 497 031 €

Duration

Start date: 2018-02-01, End date: 2023-01-31

Project acronymAMPERE

ProjectAccounting for Metallicity, Polarization of the Electrolyte, and Redox reactions in computational Electrochemistry

Researcher (PI)Mathieu Eric Salanne

Host Institution (HI)SORBONNE UNIVERSITE

Call DetailsConsolidator Grant (CoG), PE4, ERC-2017-COG

SummaryApplied electrochemistry plays a key role in many technologies, such as batteries, fuel cells, supercapacitors or solar cells. It is therefore at the core of many research programs all over the world. Yet, fundamental electrochemical investigations remain scarce. In particular, electrochemistry is among the fields for which the gap between theory and experiment is the largest. From the computational point of view, there is no molecular dynamics (MD) software devoted to the simulation of electrochemical systems while other fields such as biochemistry (GROMACS) or material science (LAMMPS) have dedicated tools. This is due to the difficulty of accounting for complex effects arising from (i) the degree of metallicity of the electrode (i.e. from semimetals to perfect conductors), (ii) the mutual polarization occurring at the electrode/electrolyte interface and (iii) the redox reactivity through explicit electron transfers. Current understanding therefore relies on standard theories that derive from an inaccurate molecular-scale picture. My objective is to fill this gap by introducing a whole set of new methods for simulating electrochemical systems. They will be provided to the computational electrochemistry community as a cutting-edge MD software adapted to supercomputers. First applications will aim at the discovery of new electrolytes for energy storage. Here I will focus on (1) ‘‘water-in-salts’’ to understand why these revolutionary liquids enable much higher voltage than conventional solutions (2) redox reactions inside a nanoporous electrode to support the development of future capacitive energy storage devices. These selected applications are timely and rely on collaborations with leading experimental partners. The results are expected to shed an unprecedented light on the importance of polarization effects on the structure and the reactivity of electrode/electrolyte interfaces, establishing MD as a prominent tool for solving complex electrochemistry problems.

Applied electrochemistry plays a key role in many technologies, such as batteries, fuel cells, supercapacitors or solar cells. It is therefore at the core of many research programs all over the world. Yet, fundamental electrochemical investigations remain scarce. In particular, electrochemistry is among the fields for which the gap between theory and experiment is the largest. From the computational point of view, there is no molecular dynamics (MD) software devoted to the simulation of electrochemical systems while other fields such as biochemistry (GROMACS) or material science (LAMMPS) have dedicated tools. This is due to the difficulty of accounting for complex effects arising from (i) the degree of metallicity of the electrode (i.e. from semimetals to perfect conductors), (ii) the mutual polarization occurring at the electrode/electrolyte interface and (iii) the redox reactivity through explicit electron transfers. Current understanding therefore relies on standard theories that derive from an inaccurate molecular-scale picture. My objective is to fill this gap by introducing a whole set of new methods for simulating electrochemical systems. They will be provided to the computational electrochemistry community as a cutting-edge MD software adapted to supercomputers. First applications will aim at the discovery of new electrolytes for energy storage. Here I will focus on (1) ‘‘water-in-salts’’ to understand why these revolutionary liquids enable much higher voltage than conventional solutions (2) redox reactions inside a nanoporous electrode to support the development of future capacitive energy storage devices. These selected applications are timely and rely on collaborations with leading experimental partners. The results are expected to shed an unprecedented light on the importance of polarization effects on the structure and the reactivity of electrode/electrolyte interfaces, establishing MD as a prominent tool for solving complex electrochemistry problems.

Max ERC Funding

1 588 769 €

Duration

Start date: 2018-04-01, End date: 2023-03-31

Project acronymAPES

ProjectAccuracy and precision for molecular solids

Researcher (PI)Jiri KLIMES

Host Institution (HI)UNIVERZITA KARLOVA

Call DetailsStarting Grant (StG), PE4, ERC-2017-STG

SummaryThe description of high pressure phases or polymorphism of molecular solids represents a significant scientific challenge both for experiment and theory. Theoretical methods that are currently used struggle to describe the tiny energy differences between different phases. It is the aim of this project to develop a scheme that would allow accurate and reliable predictions of the binding energies of molecular solids and of the energy differences between different phases.
To reach the required accuracy, we will combine the coupled cluster approach, widely used for reference quality calculations for molecules, with the random phase approximation (RPA) within periodic boundary conditions. As I have recently shown, RPA-based approaches are already some of the most accurate and practically usable methods for the description of extended systems. However, reliability is not only a question of accuracy. Reliable data need to be precise, that is, converged with the numerical parameters so that they are reproducible by other researchers.
Reproducibility is already a growing concern in the field. It is likely to become a considerable issue for highly accurate methods as the calculated energies have a stronger dependence on the simulation parameters such as the basis set size. Two main approaches will be explored to assure precision. First, we will develop the so-called asymptotic correction scheme to speed-up the convergence of the correlation energies with the basis set size. Second, we will directly compare the lattice energies from periodic and finite cluster based calculations. Both should yield identical answers, but if and how the agreement can be reached for general system is currently far from being understood for methods such as coupled cluster. Reliable data will allow us to answer some of the open questions regarding the stability of polymorphs and high pressure phases, such as the possibility of existence of high pressure ionic phases of water and ammonia.

The description of high pressure phases or polymorphism of molecular solids represents a significant scientific challenge both for experiment and theory. Theoretical methods that are currently used struggle to describe the tiny energy differences between different phases. It is the aim of this project to develop a scheme that would allow accurate and reliable predictions of the binding energies of molecular solids and of the energy differences between different phases.
To reach the required accuracy, we will combine the coupled cluster approach, widely used for reference quality calculations for molecules, with the random phase approximation (RPA) within periodic boundary conditions. As I have recently shown, RPA-based approaches are already some of the most accurate and practically usable methods for the description of extended systems. However, reliability is not only a question of accuracy. Reliable data need to be precise, that is, converged with the numerical parameters so that they are reproducible by other researchers.
Reproducibility is already a growing concern in the field. It is likely to become a considerable issue for highly accurate methods as the calculated energies have a stronger dependence on the simulation parameters such as the basis set size. Two main approaches will be explored to assure precision. First, we will develop the so-called asymptotic correction scheme to speed-up the convergence of the correlation energies with the basis set size. Second, we will directly compare the lattice energies from periodic and finite cluster based calculations. Both should yield identical answers, but if and how the agreement can be reached for general system is currently far from being understood for methods such as coupled cluster. Reliable data will allow us to answer some of the open questions regarding the stability of polymorphs and high pressure phases, such as the possibility of existence of high pressure ionic phases of water and ammonia.

Max ERC Funding

924 375 €

Duration

Start date: 2018-01-01, End date: 2022-12-31

Project acronymATOMICAR

ProjectATOMic Insight Cavity Array Reactor

Researcher (PI)Peter Christian Kjærgaard VESBORG

Host Institution (HI)DANMARKS TEKNISKE UNIVERSITET

Call DetailsStarting Grant (StG), PE4, ERC-2017-STG

SummaryThe goal of ATOMICAR is to achieve the ultimate sensitivity limit in heterogeneous catalysis:
Quantitative measurement of chemical turnover on a single catalytic nanoparticle.
Most heterogeneous catalysis occurs on metal nanoparticle in the size range of 3 nm - 10 nm. Model studies have established that there is often a strong coupling between nanoparticle size & shape - and catalytic activity. The strong structure-activity coupling renders it probable that “super-active” nanoparticles exist. However, since there is no way to measure catalytic activity of less than ca 1 million nanoparticles at a time, any super-activity will always be hidden by “ensemble smearing” since one million nanoparticles of exactly identical size and shape cannot be made. The state-of-the-art in catalysis benchmarking is microfabricated flow reactors with mass-spectrometric detection, but the sensitivity of this approach cannot be incrementally improved by six orders of magnitude. This calls for a new measurement paradigm where the activity of a single nanoparticle can be benchmarked – the ultimate limit for catalytic measurement.
A tiny batch reactor is the solution, but there are three key problems: How to seal it; how to track catalytic turnover inside it; and how to see the nanoparticle inside it? Graphene solves all three problems: A microfabricated cavity with a thin SixNy bottom window, a single catalytic nanoparticle inside, and a graphene seal forms a gas tight batch reactor since graphene has zero gas permeability. Catalysis is then tracked as an internal pressure change via the stress & deflection of the graphene seal. Crucially, the electron-transparency of graphene and SixNy enables subsequent transmission electron microscope access with atomic resolution so that active nanoparticles can be studied in full detail.
ATOMICAR will re-define the experimental limits of catalyst benchmarking and lift the field of basic catalysis research into the single-nanoparticle age.

The goal of ATOMICAR is to achieve the ultimate sensitivity limit in heterogeneous catalysis:
Quantitative measurement of chemical turnover on a single catalytic nanoparticle.
Most heterogeneous catalysis occurs on metal nanoparticle in the size range of 3 nm - 10 nm. Model studies have established that there is often a strong coupling between nanoparticle size & shape - and catalytic activity. The strong structure-activity coupling renders it probable that “super-active” nanoparticles exist. However, since there is no way to measure catalytic activity of less than ca 1 million nanoparticles at a time, any super-activity will always be hidden by “ensemble smearing” since one million nanoparticles of exactly identical size and shape cannot be made. The state-of-the-art in catalysis benchmarking is microfabricated flow reactors with mass-spectrometric detection, but the sensitivity of this approach cannot be incrementally improved by six orders of magnitude. This calls for a new measurement paradigm where the activity of a single nanoparticle can be benchmarked – the ultimate limit for catalytic measurement.
A tiny batch reactor is the solution, but there are three key problems: How to seal it; how to track catalytic turnover inside it; and how to see the nanoparticle inside it? Graphene solves all three problems: A microfabricated cavity with a thin SixNy bottom window, a single catalytic nanoparticle inside, and a graphene seal forms a gas tight batch reactor since graphene has zero gas permeability. Catalysis is then tracked as an internal pressure change via the stress & deflection of the graphene seal. Crucially, the electron-transparency of graphene and SixNy enables subsequent transmission electron microscope access with atomic resolution so that active nanoparticles can be studied in full detail.
ATOMICAR will re-define the experimental limits of catalyst benchmarking and lift the field of basic catalysis research into the single-nanoparticle age.

Max ERC Funding

1 496 000 €

Duration

Start date: 2018-02-01, End date: 2023-01-31

Project acronymATTOLIQ

ProjectAttosecond X-ray spectroscopy of liquids

Researcher (PI)Hans Jakob WÖRNER

Host Institution (HI)EIDGENOESSISCHE TECHNISCHE HOCHSCHULE ZUERICH

Call DetailsConsolidator Grant (CoG), PE4, ERC-2017-COG

SummaryCharge and energy transfer are the key steps underlying most chemical reactions and biological transformations. The purely electronic dynamics that control such processes take place on attosecond time scales. A complete understanding of these dynamics on the electronic level therefore calls for new experimental methods with attosecond resolution that are applicable to aqueous environments. We propose to combine the element sensitivity of X-ray spectroscopy with attosecond temporal resolution and ultrathin liquid microjets to study electronic dynamics of relevance to chemical, biological and photovoltaic processes. We will build on our recent achievements in demonstrating femtosecond time-resolved measurements in the water, attosecond pho-toelectron spectroscopy on a liquid microjet and measuring and controlling attosecond charge migration in isolated molecules. We will first concentrate on liquid water to study its electronic dynamics following outer-valence ionization, the formation pathway of the solvated electron and the time scales and intermolecular Coulombic decay following inner-valence or core-level ionization. Second, we will turn to solvated species and measure electronic dynamics and charge migration in solvated molecules, transition-metal complexes and pho-toexcited nanoparticles. These goals will be achieved by developing several innovative experimental tech-niques. We will develop a source of isolated attosecond pulses covering the water window (285-538 eV) and combine it with a flat liquid microjet to realize attosecond transient absorption in liquids. We will complement these measurements with attosecond X-ray emission spectroscopy, Auger spectroscopy and a novel hetero-dyne-detected variant of resonant inelastic Raman scattering, exploiting the large bandwidth that is naturally available from attosecond X-ray sources.

Charge and energy transfer are the key steps underlying most chemical reactions and biological transformations. The purely electronic dynamics that control such processes take place on attosecond time scales. A complete understanding of these dynamics on the electronic level therefore calls for new experimental methods with attosecond resolution that are applicable to aqueous environments. We propose to combine the element sensitivity of X-ray spectroscopy with attosecond temporal resolution and ultrathin liquid microjets to study electronic dynamics of relevance to chemical, biological and photovoltaic processes. We will build on our recent achievements in demonstrating femtosecond time-resolved measurements in the water, attosecond pho-toelectron spectroscopy on a liquid microjet and measuring and controlling attosecond charge migration in isolated molecules. We will first concentrate on liquid water to study its electronic dynamics following outer-valence ionization, the formation pathway of the solvated electron and the time scales and intermolecular Coulombic decay following inner-valence or core-level ionization. Second, we will turn to solvated species and measure electronic dynamics and charge migration in solvated molecules, transition-metal complexes and pho-toexcited nanoparticles. These goals will be achieved by developing several innovative experimental tech-niques. We will develop a source of isolated attosecond pulses covering the water window (285-538 eV) and combine it with a flat liquid microjet to realize attosecond transient absorption in liquids. We will complement these measurements with attosecond X-ray emission spectroscopy, Auger spectroscopy and a novel hetero-dyne-detected variant of resonant inelastic Raman scattering, exploiting the large bandwidth that is naturally available from attosecond X-ray sources.

Max ERC Funding

2 750 000 €

Duration

Start date: 2018-04-01, End date: 2023-03-31

Project acronymBioNet

ProjectDynamical Redesign of Biomolecular Networks

Researcher (PI)Edina ROSTA

Host Institution (HI)KING'S COLLEGE LONDON

Call DetailsStarting Grant (StG), PE4, ERC-2017-STG

SummaryEnzymes created by Nature are still more selective and can be orders of magnitude more efficient than man-made catalysts, in spite of recent advances in the design of de novo catalysts and in enzyme redesign. The optimal engineering of either small molecular or of complex biological catalysts requires both (i) accurate quantitative computational methods capable of a priori assessing catalytic efficiency, and (ii) molecular design principles and corresponding algorithms to achieve, understand and control biomolecular catalytic function and mechanisms. Presently, the computational design of biocatalysts is challenging due to the need for accurate yet computationally-intensive quantum mechanical calculations of bond formation and cleavage, as well as to the requirement for proper statistical sampling over very many degrees of freedom. Pioneering enhanced sampling and analysis methods have been developed to address crucial challenges bridging the gap between the available simulation length and the biologically relevant timescales. However, biased simulations do not generally permit the direct calculation of kinetic information. Recently, I and others pioneered simulation tools that can enable not only accurate calculations of free energies, but also of the intrinsic molecular kinetics and the underlying reaction mechanisms as well. I propose to develop more robust, automatic, and system-tailored sampling algorithms that are optimal in each case. I will use our kinetics-based methods to develop a novel theoretical framework to address catalytic efficiency and to establish molecular design principles to key design problems for new bio-inspired nanocatalysts, and to identify and characterize small molecule modulators of enzyme activity. This is a highly interdisciplinary project that will enable fundamental advances in molecular simulations and will unveil the physical principles that will lead to design and control of catalysis with Nature-like efficiency.

Enzymes created by Nature are still more selective and can be orders of magnitude more efficient than man-made catalysts, in spite of recent advances in the design of de novo catalysts and in enzyme redesign. The optimal engineering of either small molecular or of complex biological catalysts requires both (i) accurate quantitative computational methods capable of a priori assessing catalytic efficiency, and (ii) molecular design principles and corresponding algorithms to achieve, understand and control biomolecular catalytic function and mechanisms. Presently, the computational design of biocatalysts is challenging due to the need for accurate yet computationally-intensive quantum mechanical calculations of bond formation and cleavage, as well as to the requirement for proper statistical sampling over very many degrees of freedom. Pioneering enhanced sampling and analysis methods have been developed to address crucial challenges bridging the gap between the available simulation length and the biologically relevant timescales. However, biased simulations do not generally permit the direct calculation of kinetic information. Recently, I and others pioneered simulation tools that can enable not only accurate calculations of free energies, but also of the intrinsic molecular kinetics and the underlying reaction mechanisms as well. I propose to develop more robust, automatic, and system-tailored sampling algorithms that are optimal in each case. I will use our kinetics-based methods to develop a novel theoretical framework to address catalytic efficiency and to establish molecular design principles to key design problems for new bio-inspired nanocatalysts, and to identify and characterize small molecule modulators of enzyme activity. This is a highly interdisciplinary project that will enable fundamental advances in molecular simulations and will unveil the physical principles that will lead to design and control of catalysis with Nature-like efficiency.

Max ERC Funding

1 499 999 €

Duration

Start date: 2018-02-01, End date: 2023-01-31

Project acronymCM3

ProjectControlled Mechanical Manipulation of Molecules

Researcher (PI)Christian Wagner

Host Institution (HI)FORSCHUNGSZENTRUM JULICH GMBH

Call DetailsStarting Grant (StG), PE4, ERC-2017-STG

SummaryThe idea to freely control the atomic-scale structure of matter has intrigued scientists for many decades. The low-temperature scanning probe microscope (LT SPM) has become the instrument of choice for this task since it allows the rearrangement of atoms and molecules on a surface. There is, however, no generic SPM-based method for the manipulation of molecules beyond lateral rearrangement. The goal of this project is to develop controlled mechanical manipulation of molecules (CM3) in which a LT SPM is used to handle large organic molecules in three dimensions with optimal control over position, orientation and shape. CM3 will become a game-changing technique for research on molecular properties and molecular-scale engineering, because it combines fully deterministic manipulation with broad access to molecular degrees of freedom for the first time. In CM3 the tip is attached to a single reactive atom within a molecule. Tip displacement guides the molecule into a desired conformation while the surface provides a second (weaker) fixation. The fundamental challenge addressed by this project is the identification of precise molecular conformations at any time during manipulation. The solution is a big data approach where large batches of automatically recorded SPM manipulation data are structured using machine learning and interpreted by comparison to atomistic simulations. The key idea is a comparison of entire conformation spaces at once, which is robust, even if the theory is not fully quantitative. The obtained map of the conformation space is used to determine molecular conformations during manipulation by methods of control theory. The effectiveness of this approach will be demonstrated in experiments that unambiguously reveal the structure-conductance relation for a series of molecules and that realize the engineering paradigm of piecewise assembly on the molecular scale by constructing a direct current rotor / motor from individual components.

The idea to freely control the atomic-scale structure of matter has intrigued scientists for many decades. The low-temperature scanning probe microscope (LT SPM) has become the instrument of choice for this task since it allows the rearrangement of atoms and molecules on a surface. There is, however, no generic SPM-based method for the manipulation of molecules beyond lateral rearrangement. The goal of this project is to develop controlled mechanical manipulation of molecules (CM3) in which a LT SPM is used to handle large organic molecules in three dimensions with optimal control over position, orientation and shape. CM3 will become a game-changing technique for research on molecular properties and molecular-scale engineering, because it combines fully deterministic manipulation with broad access to molecular degrees of freedom for the first time. In CM3 the tip is attached to a single reactive atom within a molecule. Tip displacement guides the molecule into a desired conformation while the surface provides a second (weaker) fixation. The fundamental challenge addressed by this project is the identification of precise molecular conformations at any time during manipulation. The solution is a big data approach where large batches of automatically recorded SPM manipulation data are structured using machine learning and interpreted by comparison to atomistic simulations. The key idea is a comparison of entire conformation spaces at once, which is robust, even if the theory is not fully quantitative. The obtained map of the conformation space is used to determine molecular conformations during manipulation by methods of control theory. The effectiveness of this approach will be demonstrated in experiments that unambiguously reveal the structure-conductance relation for a series of molecules and that realize the engineering paradigm of piecewise assembly on the molecular scale by constructing a direct current rotor / motor from individual components.

SummaryCollagen mineralization in bone is one of the most crucial processes in our body as it supplies the skeleton on which we depend for support and protection. Bone’s impressive mechanical properties arise from the hierarchical organization of the organic collagen matrix that is mineralized with ultrathin, aligned inorganic crystals of carbonated hydroxyapatite.
Despite its importance to the human body, relatively little is understood about collagen mineralization and how the proteins govern mineral growth with such precision. This is because the matrix development is a complex process with different stages that occur over multiple length scales and depends on many different components.
I propose to obtain the first comprehensive picture of the collagen mineralization mechanism by unraveling its dynamics and structural details. It is not only of great fundamental importance, it also opens the way to the development of better biomaterials, as well as to strategies for the treatment of mineralization-related diseases.
I will achieve this ambitious goal by designing a dedicated tissue engineering platform that models real bone as closely as possible, and will allow application of multiple advanced analysis techniques. These I will employ in a “Google Earth” approach, studying the process from the micrometer to the nanometer scale, combining live cell imaging and “beyond state-of-the-art” electron microscopy with chemical and biochemical analysis to reveal the details of collagen mineralization with the highest spatial, temporal and molecular resolution thus far. Exploiting my extensive expertise in the field of biomineralization and advanced electron microscopy, COLMIN will provide a major step in understanding collagen formation and mineralization, and provide insights that will help to fight bone-related diseases. The advanced multidisciplinary methodology developed here will set a new standard for the advanced analysis of bone formation and other biological processes.

Collagen mineralization in bone is one of the most crucial processes in our body as it supplies the skeleton on which we depend for support and protection. Bone’s impressive mechanical properties arise from the hierarchical organization of the organic collagen matrix that is mineralized with ultrathin, aligned inorganic crystals of carbonated hydroxyapatite.
Despite its importance to the human body, relatively little is understood about collagen mineralization and how the proteins govern mineral growth with such precision. This is because the matrix development is a complex process with different stages that occur over multiple length scales and depends on many different components.
I propose to obtain the first comprehensive picture of the collagen mineralization mechanism by unraveling its dynamics and structural details. It is not only of great fundamental importance, it also opens the way to the development of better biomaterials, as well as to strategies for the treatment of mineralization-related diseases.
I will achieve this ambitious goal by designing a dedicated tissue engineering platform that models real bone as closely as possible, and will allow application of multiple advanced analysis techniques. These I will employ in a “Google Earth” approach, studying the process from the micrometer to the nanometer scale, combining live cell imaging and “beyond state-of-the-art” electron microscopy with chemical and biochemical analysis to reveal the details of collagen mineralization with the highest spatial, temporal and molecular resolution thus far. Exploiting my extensive expertise in the field of biomineralization and advanced electron microscopy, COLMIN will provide a major step in understanding collagen formation and mineralization, and provide insights that will help to fight bone-related diseases. The advanced multidisciplinary methodology developed here will set a new standard for the advanced analysis of bone formation and other biological processes.

Max ERC Funding

3 498 006 €

Duration

Start date: 2019-01-01, End date: 2023-12-31

Project acronymeDrop

ProjectDroplet Photoelectron Imaging

Researcher (PI)Ruth Signorell Luckhaus

Host Institution (HI)EIDGENOESSISCHE TECHNISCHE HOCHSCHULE ZUERICH

Call DetailsAdvanced Grant (AdG), PE4, ERC-2017-ADG

SummaryAngle-resolved photoelectron spectroscopy of aerosol droplets (“droplet photoelectron imaging”) is a novel approach to study fundamental aspects of the electron dynamics in liquids and across interfaces. Our recent proof-of-principle studies demonstrate that droplet photoelectron imaging not only complements, but also significantly extends the range of accessible information over established methods. Two aspects are unique to droplets: Firstly, the droplet size can be varied over a wide range from submicrons to microns. While large droplets provide overlap with liquid microjet and bulk studies, small droplets offer additional control by acting as efficient optical resonators. These optical cavity effects can be exploited to control where in the droplet the photoelectrons are generated; e.g. surface versus volume. Secondly, comprehensive information about photoelectron kinetic energy and angular distributions can be obtained fast and in a straightforward way by velocity map imaging.
Building on our proof-of-principle studies, we propose to exploit the versatility of the droplet approach to address fundamental questions regarding electron dynamics in liquids and across interfaces: Can this new tool provide the missing data for low-energy electron scattering in water and other liquids and resolve the issue of the “universal curve”? How do slow electrons scatter across liquid-gas and buried liquid-liquid/solid interfaces and how does this depend on the composition and curvature of the interface? How is the ultrafast relaxation dynamics of electrons following above-band-gap excitation influenced by electron scattering and confinement effects? Low-energy electron scattering is a determining factor in radiation chemistry and biology and a central aspect of the solvated electron dynamics, while interfacial processes play a key role in atmospheric aerosols. Droplet photoelectron imaging opens up new ways to study such phenomena.

Angle-resolved photoelectron spectroscopy of aerosol droplets (“droplet photoelectron imaging”) is a novel approach to study fundamental aspects of the electron dynamics in liquids and across interfaces. Our recent proof-of-principle studies demonstrate that droplet photoelectron imaging not only complements, but also significantly extends the range of accessible information over established methods. Two aspects are unique to droplets: Firstly, the droplet size can be varied over a wide range from submicrons to microns. While large droplets provide overlap with liquid microjet and bulk studies, small droplets offer additional control by acting as efficient optical resonators. These optical cavity effects can be exploited to control where in the droplet the photoelectrons are generated; e.g. surface versus volume. Secondly, comprehensive information about photoelectron kinetic energy and angular distributions can be obtained fast and in a straightforward way by velocity map imaging.
Building on our proof-of-principle studies, we propose to exploit the versatility of the droplet approach to address fundamental questions regarding electron dynamics in liquids and across interfaces: Can this new tool provide the missing data for low-energy electron scattering in water and other liquids and resolve the issue of the “universal curve”? How do slow electrons scatter across liquid-gas and buried liquid-liquid/solid interfaces and how does this depend on the composition and curvature of the interface? How is the ultrafast relaxation dynamics of electrons following above-band-gap excitation influenced by electron scattering and confinement effects? Low-energy electron scattering is a determining factor in radiation chemistry and biology and a central aspect of the solvated electron dynamics, while interfacial processes play a key role in atmospheric aerosols. Droplet photoelectron imaging opens up new ways to study such phenomena.

SummaryLanthanide metals are ubiquitous nowadays, finding use in luminescent materials, optical amplifiers and waveguides, lasers, photovoltaics, rechargeable batteries, catalysts, alloys, magnets, bio-probes, and therapeutic agents. In addition, they bear potential for high temperature superconductivity, magnetic refrigeration, molecular magnetic storage, spintronics and quantum information.
Surprisingly, the study of lanthanide physico-chemical properties on surfaces is at its infancy, particularly at the nanoscale. To address this extraordinary scientific opportunity, I will research the foundations and prospects of lanthanide elements to design functional nanoarchitectures on surfaces and I will study their inherent physico-chemical phenomena in distinct coordination environments, targeting novel approaches for sensing, nanomagnetism and electroluminescence. Importantly, our studies will encompass both metal substrates and decoupling surfaces including ultra-thin film insulators and graphene. Nurturing from these studies and in parallel, we will focus on graphene voltage back-gated supports, thus surpassing the seminal knowledge on electrically-inert substrates and enhancing the scope of our research to address the overarching objective of the proposal, i.e., the design of electrically tunable functional lanthanide nanomaterials.
The culmination of ELECNANO project will provide strategies for:
1.-Design of functional nanomaterials on high-technological supports.
2.-Development of advanced coordination chemistry on surfaces.
3.-Rationale of the physico-chemical properties of lanthanide-coordination environments.
4.-Engineering of lanthanide nanoarchitectures for ultimate sensing, nanomagnetism and electroluminescence.
5.-In-situ atomistic views of electrically tunable materials and unprecedented fundamental studies of charge-molecule/metal physics on devices.

Lanthanide metals are ubiquitous nowadays, finding use in luminescent materials, optical amplifiers and waveguides, lasers, photovoltaics, rechargeable batteries, catalysts, alloys, magnets, bio-probes, and therapeutic agents. In addition, they bear potential for high temperature superconductivity, magnetic refrigeration, molecular magnetic storage, spintronics and quantum information.
Surprisingly, the study of lanthanide physico-chemical properties on surfaces is at its infancy, particularly at the nanoscale. To address this extraordinary scientific opportunity, I will research the foundations and prospects of lanthanide elements to design functional nanoarchitectures on surfaces and I will study their inherent physico-chemical phenomena in distinct coordination environments, targeting novel approaches for sensing, nanomagnetism and electroluminescence. Importantly, our studies will encompass both metal substrates and decoupling surfaces including ultra-thin film insulators and graphene. Nurturing from these studies and in parallel, we will focus on graphene voltage back-gated supports, thus surpassing the seminal knowledge on electrically-inert substrates and enhancing the scope of our research to address the overarching objective of the proposal, i.e., the design of electrically tunable functional lanthanide nanomaterials.
The culmination of ELECNANO project will provide strategies for:
1.-Design of functional nanomaterials on high-technological supports.
2.-Development of advanced coordination chemistry on surfaces.
3.-Rationale of the physico-chemical properties of lanthanide-coordination environments.
4.-Engineering of lanthanide nanoarchitectures for ultimate sensing, nanomagnetism and electroluminescence.
5.-In-situ atomistic views of electrically tunable materials and unprecedented fundamental studies of charge-molecule/metal physics on devices.